Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate

Definitions

• the present invention relates to a transparent thermoplastic resin composition capable of blocking light having a particular wavelength and to a molded article of the same, more specifically, to a transparent thermoplastic resin composition that is utilized in the fields of optical, electric and electronic appliances and medical materials etc. and has the ability to absorb light of 410 nm in wavelength, and to a molded article of the same.
• Light of 410 nm in wavelength has noticeable photoinduction property for noxious inspects. If a material capable of blocking light of 410 nm in wavelength which is transparent and thermoplastic can be developed, it is applied to, for example, lighting apparatus covers, which can lead to lighting apparatuses having excellent mothproof property. Therefore, development of such materials has been awaited.
• polycarbonate resins have excellent impact and heat resistances, and are widely used in various fields.
• the resins are somewhat problematic in terms of weathering resistance: undesired yellowish discoloration and other problems may occur when they are irradiated not only with normal solar source but also with light from high pressure mercury vapor lamps and metal halide lamps.
• a polycarbonate resin composition prepared by adding an ultraviolet absorber comprising a benzotriazole compound and a fluorescent whitening agent selected from coumarin compounds and naphthalimide compounds to a polycarbonate resin is proposed (Patent document 1).
• a polycarbonate resin composition prepared by adding an ultraviolet absorber comprising a triazine compound and a fluorescent whitening agent selected from coumarin compounds and naphthalimide compounds to a polycarbonate resin is also proposed (Patent document 2).
• thermoplastic resin composition having both transparency and weathering resistance
• An improvement in weathering resistance is intended by adding a fine powder of titanium oxide (TiO 2 ) or zinc oxide (ZnO) (Patent documents 3 and 4), but sufficient transparency has not been obtained.
• a film whose transparency is ensured by adding a fine powder of zinc oxide is proposed (Patent document 5).
• a thermoplastic resin composition containing an ultraviolet absorber and a fine powder of titanium oxide or zinc oxide in a resin composition such as polycarbonate is proposed as a thermoplastic resin composition having both transparency and weathering resistance (Patent document 6).
• resin compositions comprising an ultraviolet absorber and a thermoplastic resin are already known, but no transparent resin composition which can effectively absorb and block light in the boundary region of the visible light region and the ultraviolet light region is known.
• light of 410 nm in wavelength has noticeable photoinduction property for noxious inspects. If a transparent material capable of blocking light of 410 nm in wavelength is developed, it will be used widely in the fields of optics, electrics and electronics, medical materials and the like, for example, lighting apparatuses having excellent mothproof property and other products. Under such background, development of a material which shuts off light of 410 nm in wavelength is strongly desired.
• Patent document 1 Japanese Patent Application Publication No. H07-196904
• Patent document 2 Japanese Patent Application Publication No. H10-176103
• Patent document 5 Japanese Patent Application Publication No. 2000-309100
• An object of the present invention is to provide a thermoplastic resin composition which has excellent transparency and the ability to shut off the light of 410 nm in wavelength and a molded article of the same.
• thermoplastic transparent composition which has excellent transparency and the ability to shut off light of 410 nm in wavelength and a molded article of the same can be obtained by adding a specific amount of an ultraviolet absorber having a specific absorption band to a transparent thermoplastic resin such as polycarbonate.
• to shut off light of 410 nm in wavelength means to make a transmission coefficient of 410 nm-light 1% or lower in a molded article having a predetermined thickness. This is because sufficient mothproof property cannot be obtained if the transmission coefficient of 410 nm-light is higher than 1%.
• the present invention was accomplished on a basis of such findings.
• the present invention provides the following thermoplastic transparent compositions and molded articles of the same.
• Examples of the transparent thermoplastic resin of the component (A) in the present invention include polycarbonate resins, polyolefin resins such as polyethylene, polypropylene and polybutylene, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polyvinyl alcohol resins, chlorinated polyethylene resins, ethylene- ⁇ -olefin copolymers, propylene- ⁇ -olefin copolymers, ethylene-vinyl chloride copolymers, ethylene-vinyl acetate copolymers, ethylene tetrafluoride-ethylene copolymers, ethylene tetrafluoride-propylene hexafluoride copolymers, vinyl polyfluoride resins, polyvinylidene difluoride resins, transparent polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins and the like. These may be used singly or in combination of two or more kinds.
• polycarbonate resins their chemical structures and production methods are not particularly limited and various substances can be used.
• aromatic polycarbonate resins produced by a reaction between a divalent phenol and a carbonate precursor can be suitably used.
• Suitable substances can be used as the above-mentioned divalent phenol. Suitable examples include 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl )propane, 4,4′-dihydroxydiphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl )sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, hydroquinone, resorcin, catechol and the like.
• divalent phenols bis(hydroxyphenyl)alkane, in particular 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] is preferred.
• bis(hydroxyphenyl)alkane in particular 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] is preferred.
• bisphenol A 2,2-bis(4-hydroxyphenyl)propane
• carbonate precursors usable for a reaction with a divalent phenol are carbonyl halides, carbonyl esters, or haloformates and the like. More specifically, phosgene, dihaloformates of divalent phenols, diphenyl carbonates, dimethyl carbonates and diethyl carbonates can be used.
• the chemical structure of this polycarbonate resin can be such that its molecular chain has a linear structure, a cyclic structure or a branched structure.
• suitable examples of polycarbonate resins having a branched structure include those produced by using, as a branching agent, 1,1,1 -tris(4-hydroxyphenyl)ethane, ⁇ , ⁇ ′, ⁇ ′′-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, phloroglucin, trimellitic acid, isatinbis(o-cresol) and the like.
• polyester-carbonate resins produced by using bifunctional carboxylic acids such as terephthalic acid or their ester precursors such as ester forming derivatives can be also used. Furthermore, mixtures of these polycarbonate resins having various chemical structures can be also used.
• the viscosity average molecular weight of these polycarbonate resins is normally 10,000 to 50,000, preferably 13,000 to 35,000, more preferably 15,000 to 25,000.
• phenol p-tert-butylphenol, p-dodecylphenol, p-tert-octylphenol, p-cumylphenol and the like are used.
• polycarbonate-polyorganosiloxane copolymers can be further used.
• This copolymer can be prepared by, for example, dissolving polycarbonate oligomer and polyorganosiloxane having a terminal reactive group in a solvent such as methylene chloride, adding an aqueous solution of divalent phenol in sodium hydroxide to this solution, and causing an interface polycondensation reaction by using a catalyst such as triethylamine.
• a polyorganosiloxane structure portion in this case that having polydimethyl siloxane structure, polydiethyl siloxane structure, polymethylphenyl siloxane structure, polydiphenyl siloxane structure is suitably used.
• this polycarbonate-polyorganosiloxane copolymer used is suitably such that the degree of polymerization of the polycarbonate portion is 3 to 100 and the degree of polymerization of the polyorganosiloxane portion is approximately 2 to 500.
• the amount of the polyorganosiloxane portion contained in this polycarbonate-polyorganosiloxane copolymer is suitably 0.5 to 30% by mass, preferably 0.5 to 20% by mass.
• the viscosity average molecular weight of this polycarbonate-polyorganosiloxane copolymer is 10,000 to 50,000, preferably 13,000 to 35,000, and more preferably 15,000 to 25,000.
• the ultraviolet absorber of the component (B) used in the present invention has an absorption band in the range of at least 340 to 410 nm, when determined in a chloroform solution.
• the phrase “to have an absorption band in the range at least of 340 to 410 nm” means that an absorbance determined by a spectrophotometer (calculated from the strength of a transmission light relative to incident light) falls within the range of the absorption band.
• Examples of such ultraviolet absorbers include benzophenone-based compounds, benzotriazole-based compounds, benzoate compounds, cyanoacrylate-based compounds and the like, among which benzotriazole-based compounds and benzoate compounds are more preferable, and in particular benzoate compounds are preferable.
• the amount added is 0.3 to 3.0 parts by mass, preferably 0.5 to 2.5 parts by mass, more preferably 1.0 to 2.0 parts by mass relative to 100 parts by mass of the transparent thermoplastic resin.
• a resin composition having a good absorptivity for light of 410 nm in wavelength can be obtained by adding 0.3 to 3.0 parts by mass of an ultraviolet absorber having an absorption band in the range at least of 340 to 410 nm.
• benzophenone-based compounds used as the above-mentioned ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-ethoxy-benzophenone and the like.
• benzotriazole-based compound examples include 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole, 2-(2′-hydroxy-5′-tert-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole, 2-[2′-hydroxy-3′,5′-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2′-methylene-bis[4-methyl6-(benzotriazole-2-yl)phenol] and the like.
• benzoate compound examples include diethylamino hydroxybenzoyl hexyl benzoate, methylethylamino hydroxybenzoyl hexyl benzoate, dimethylamino hydroxybenzoyl hexyl benzoate, ethylpropylamino hydroxybenzoyl hexyl benzoate, dipropylamino hydroxybenzoyl hexyl benzoate and the like.
• cyanoacrylate-based compounds include 2-ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate,
• a compound obtained by graft-polymerizing an ultraviolet-absorbing unit on an acrylic polymer can be also used as the ultraviolet absorber of the component (B).
• This compound has a structure in which an ultraviolet-absorbing unit having an ultraviolet absorptivity is introduced into a polymer chain of the acrylic polymer by graft polymerization (hereafter referred to as “high-molecular ultraviolet absorber”).
• acrylic monomer constituting this acrylic polymer include acrylic acid, methacrylic acid, alkyl acrylate esters, alkyl methacrylate esters, acrylamide, methacrylamide, copolymerized polymers of these acrylic monomers and copolymerizable vinyl compounds having a double bond and the like.
• this copolymerizable vinyl compounds include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate, alkyl vinyl esters such as ethylvinyl and 2-ethylhexylvinyl; styrene, maleic anhydride and the like.
• the number average molecular weights of these acrylic polymers are 20,000 to 200,000, and preferably 50,000 to 200,000.
• An ultraviolet-absorbing unit introduced into this acrylic polymer may be any compound that has an ultraviolet absorptivity. Examples include the aforementioned benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, benzoate compounds and the like. These compounds are introduced into polymer chains of acrylic polymers by graft polymerization. In this case, the amount of the ultraviolet-absorbing unit introduced into the acrylic polymer is 40 to 90% by mass, preferably 50 to 80% by mass of the total mass of the ultraviolet absorber.
• Preferable high-molecular ultraviolet absorbers are those in which the ultraviolet-absorbing unit is a benzotriazole compound or a benzoate compound, especially a benzoate compound, and the number average molecular weight of the acrylic polymer is 50,000 to 200,000.
• the high-molecular ultraviolet absorbers may be used singly or in combination of two or more kinds, and can be also used in combination with the aforementioned ultraviolet absorbers.
• a stabilizer antioxidant, dispersing agent, etc.
• mold releasing agent coloring agent (dye, pigment) and other additives
• antioxidants include phenol-based antioxidants such as pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl )propionate]; phosphorus-based antioxidants such as phosphite esters and tris(2,4-di-t-butylphenyl)phosphite; and sulfur-based antioxidants such as dilauryl-3,3′-thiodipropionate.
• dispersing agents include magnesium stearate and the like.
• mold releasing agents include monoglycerin stearate, polyethylene tetrastearate and the like.
• the antioxidant and mold releasing agent may contain a radical scavenger and an acid neutralizer.
• a coloring agent a generally used pigment or the like is used. The amount of these additives added is preferably 1 part by mass or less based on 100 parts by mass of the thermoplastic resin composition.
• the above additives may be added to the above components (A) and (B) in an amount suitable for required characteristics of a molded article and kneaded.
• Blenders and kneaders used herein are those normally used.
• a ribbon blender, drum tumbler and the like can be used to carry out pre-mix, and a Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, multiple screw extruder, Ko-kneader or the like may be used.
• the heating temperature in kneading is normally selected from the range from 240 to 300° C. suitably.
• an extrusion molder in particular a vented extrusion molder is preferably used.
• the components other than the thermoplastic resin contained can be fused and kneaded with the thermoplastic resin in advance, that is, can be added as a master batch.
• thermoplastic resin composition of the present invention can be used as a raw material in the form of a kneaded product obtained by the above-mentioned fusion kneading molding or pellets to produce various kinds of molded articles by injection molding, injection-compression molding, extrusion molding, blow molding, press molding, foam molding or other methods.
• especially preferable is the method of fusing and kneading the components mentioned above to produce a pelletized molding raw material, and then producing injection molded articles by injection molding or injection-compression molding with these pellets.
• employing the gas injection molding as this injection molding can give a molded article which has no sink mark but has excellent appearance and reduced weight.
• thermoplastic transparent composition of the present invention By forming the thermoplastic transparent composition of the present invention, a molded article capable of blocking light of 410 nm in wavelength and having transparency, for example, a molded article in which a transmission coefficient of light of 410 nm in wavelength is 1.0% or lower and a haze value is 2% or lower in a molded article having a thickness of 0.8 mm, or a molded article in which a transmission coefficient of light of 410 nm in wavelength is 1% or lower and a haze value is 2% or lower in a molded article having a thickness of 2 mm can be obtained.
• a molded article with a laminated structure can be obtained by co-extruding the thermoplastic resin composition of the present invention and another transparent thermoplastic resin.
• a molded article with a laminated structure can be also obtained by extruding the thermoplastic resin composition of the present invention and another transparent thermoplastic resin separately to form molded articles, and bonding the obtained separate molded articles together.
• thermoplastic transparent composition of the present invention can be widely used in the fields of optics, electrics and electronics, medical materials, for example, for lighting apparatus covers, sunglass lenses, photoresists, transparent office automation equipment, housings for electric or electronic appliances and various medical materials.
• the (B) ultraviolet absorbers used in Table 1 are as follows:
• Table 1 reveals the followings:
• thermoplastic transparent composition which has excellent absorptivity of light of 410 nm in wavelength and a molded article of the same can be provided by adding a specific amount of an ultraviolet absorber having a specific absorption band to a transparent thermoplastic resin such as polycarbonate.
• thermoplastic transparent composition of the present invention can be widely used in the fields of optics, electrics, electronics, medical materials and others.
• it can be formed into a lighting apparatus cover to provide a lighting apparatus having excellent mothproof property.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Laminated Bodies (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 2006
  • 2006-01-18 JP JP2007503596A patent/JP5086802B2/ja not_active Expired - Fee Related
  • 2006-01-18 US US11/816,447 patent/US20090208755A1/en not_active Abandoned
  • 2006-01-18 DE DE200611000415 patent/DE112006000415T5/de not_active Withdrawn
  • 2006-01-18 CN CN2006800052508A patent/CN101120051B/zh not_active Expired - Fee Related
  • 2006-01-18 WO PCT/JP2006/300592 patent/WO2006087882A1/ja not_active Application Discontinuation
  • 2006-01-24 TW TW95102678A patent/TWI400298B/zh not_active IP Right Cessation

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